Photographic light sensitive elements containing azanol dyes



March 13, 1951 A. w. ANISH ET AL 2,545,421

PHOTOGRAPHIC 1.12m SENSITIVE ELEMENTS CONTAINING AZANOL DYES Original Filed Oct. 5, 1946 EMULSION CON T/HN/NG DYE OF EXAMPLE 1' FIG. 1

EMuLs/oN CONTAINING DYE OF EXAMPLE 12' FIG. 2

EMULS/ON CONTAIN/N6 DYE OF EXAMPLE HZ FIG. 3

EMULSION co/vm/w/vc DYE OF EXAMPLE I FIG. 4

54 as 42 45 50 54 5e 62 EMULSION con/mum's DXE OF EXAMPLE :zr

FIG. 5

ALFRED W AN/SH LEE C. HENSLEY INVENTORS I TTORNEY Patented Mar. 13, 1951 PHOTOGRAPHIC LIGHT SENSITIVE ELE- MENTS CONTAINING AZANOL DYES Alfred W. Anish, Vestal, and Lee C. Hensley,

Binghamton, N. Y., assignors to General Aniline & Film Corporation, New York, N. Y., a

corporation of Delaware Original application October 5, 1946, Serial No. 701,424. Divided and this application August 11, 1949, Serial No. 109,684

This invention relates to sensitizing dyes for light-sensitive photographic elements, and particularly to azanol dyes as sensitizers for silver halide emulsions.

sensitizing dyes, comprising two heterocyclic nitrogenous nucleilinked by a chain of atoms including one or more nitrogen atoms, are known. These dyes are prepared by condensing a quaternary cyclammonium cyanine dye intermediate, containing an active group in the alpha or gamma position, with a diamine, such as, for example, hydrazine, ethylene diamine, p-phenylene diamine, and the like. These condensation products are, for the most part, insoluble in aqueous solutions of inorganic bases and do not form metal salts with such bases. Moreover, these prczducts are incapable of forming heavy metal sal s.

We have discovered that by condensing a 5- or 6-membered keto-heterocyclic compound, containing a reactive group, with an aliphatic, aromatic or heterocyclic diamine while'heating in the presence of an alcohol as a solvent-diluent with or without a tertiary base, new dyes are obtained which are not only soluble in aqueous solutions of inorganic bases, but also form stable heavy metal salts, particularly silver salts. The silver salts are non-diffusing and readily dis- 9 Claims.

chargeable in the usual processing baths. These 1 Accordingly, it is an object of the present invention to provide a new class of azanol dyes as sensitizing dyes for light sensitive photographic elements.

A further object is to provide sensitizing dyes which have no deleterious effect on the photographic properties of the film.

Other objects and advantages of this invention will become apparent by reference to the following specification in which its preferred details and embodiments are described. Y 'The azanol dyes prepared according to the present invention are characterized by the followinggeneral formula: p b

I \C QH HO C7 wherein A represents the atoms necessary to complete a 5-membered or 6-membered heterocyclic nucleus, e. g., of a barbituric acid, a thio-barbituric acid, arhodanine, an oxazoledione, a thiozolone, a pyrazolone, a hydantoin, a, thiohydantoin, and the like, n represents a positive odd integer not greater than 3, and N--X-N is the radical of a primary diamine, said diamine being hydrazine, an aliphatic, aromatic, or heterocyclic diamine containing not more than 14 carbon atoms,

For instance, when the primary diamine is ar'owherein Ar represents an aromatic radical containing up to 12 carbon atoms.

The process of preparing the above azanol dyes comprises heating, preferably under refluxconditions, with or without a tertiary base", an alcoholic solution of hydrazine, or analiphatic, aromatic or heterocyclic diamine with a 5-membered or 6-membered heterocyclic intermediate derived from a barbituric acid, a thiobarbituric acid, a rhodanine, a hydantoin, a thiohydantoin, an oxazoledione, a thiazolone, a pyrazolone, and the like, having a reactive acetanilido group linked to a carbon atom of a monoor polymethine chainof not more than 3 carbon atoms adjacent to a keto group of such intermediate.

The diamines used in the preparation of the new dyes of the present invention, and having the general formula:

Hydrazine I Ethylenediamine 2,545,421 1 3 4 whe n A a d n v e same si nificance as during which time the dye separated from the above. As illustrative of compounds represe hot alcohol. The mixture was filtered while hot, by this general formula, reference is made to: and the filter residue boiled out twice with 100 cc, portions of methanol. The dye. was further purified by dissolving it in Ni/lecaustic solution, filtering the solution carefully, and precipitating with dilute acetic acid.

The dye sensitized a silver chlorobromide emulsion to 590. ma,v with a maximum at 545 m 4 e ('y acetanilidoallylidene) e 1 (2) benzoe thiazolyl 3 methyl 5 pyrazolone 4 acetanilidomethylene 3 methyl 1 phenyl- 5-pyrazolone 4 ('y acetanilidoallylidenel methyl e. 1

phenyl-S-pyrazolone V 4 acetanilidomethylene 3 methyl 1 (2) Exampl I pyridyl-5-pyrazolone 3 acetanilidomethylene 5 methyl thiophen v -fi? 2-one s=o Q1011; HO-C o:s 5-acetanilidomethylene-3-allylrhodanine 5-acetanilidopropanylidene-3-allylrhodanine 5-acetanilidomethylene-S-phenylrhodanine 7 C335 5-acetanilidomethylene-3-ethylrhodanine In a manner similar to that used in the prep-- 5 acetanilidomethylene 3 ethyl 2 e thie- '5 aration of the dye described in Example I, 0.4 2,4(3,5) -oxazoledione gram of benzidine was reacted with 1.2 grams of 5 1 ae t nili ally d n 2 e d ph nyl 5-aceii m idomethtllene-3-allylrhodanine. -Thi,s amino-1(5) -.th iazolone dye. sensitized a silver chlorobromide emulsion to,

5 s (a; acetanilidoallylidene) e 3. e ethyl 2 5 70 m l, with a maximum 21115.20 ma. .-thio-2,4(3,5)-oxazoledione 5 acetanilidoallylidene) a ethyl 1 Example phenyl-Z-thiohydantoin SFCFQHzN I 7 CH2 s 5 (5 acetanilido A2,4 pentadienyliden I I H O G H sec HO-C 3-ethylrhodanine v S 5 ('y acetanilidoallylidene) 2,4,6 triketov hexahydropyrimidine Q Ht eHs 3Q 5 2 By reacting 0.4. gram of p.p"-cliamino-dipheny1-, dike-t0hexahy ropyrimid nei 3 1d t i llke, methana it 1 2 grams of 5 t 1 d 1 As solvenbdiluents employed in the pfeparafi; ene-S-allylrhodarfinein isopropyl alcohol, accorde".

tion of the new dyes of the present invention, mg to the method of Example a yellow the following alcohols may be employed: methyl, was obtained EIZhiS dye sensitize? silver ethyl, propyl, isopropyl, butyl, benzyl, furfuryl robmlmd-eemulslon to 530 mm a alcohol, and the like. Triethylamine, tributyl-i amine, and the like are representative of the ter.-. I Example IV tiary bases which We may use.

When 1 mol of a diamine, of the type men-s 40 HO-1G-QH=N' =QHCCH tioned above, is condensed with 1 mol of a 5-- J J '5 HaQ- 0 0H H0 0 .-CH&' membered or fi-membered heterocyclic mtermediate in the presence of an alcohol, with or withv out a tertiary base as a catalyst,' a reaction 00- While following the procedure f xample L0 ours which may be Written as follows: r f p-ph ny ne d min d 10 0 gr ms f 6661?; 666": a A I E at o =o o= -oH=).-iN N-XN9 Ni- -oH=).=(i-o=o ll i' l i i I l TELL T511292 \s \z v i ',C,(CH=)..=N--X-N=(--CH=),\C\ '4 ll ll i ooH HQ-CV:

The following examples describe in detail the ac la ilidome hyl ne 5- L 'JZWI- lt i ip lerl-'2 methods for accompli hing the above objects but ne were reacted 11115 q- 0 isopropyl alcohol in, it is to be understood that; they are inserted G1 the presence of 1 co, 01: triethylamine. ".I le relmerely for the purpose or illustration and are not suiting dy se s t zed a silver chlombromide,

be construed as limitative. 611111151011 0- 3 mm with a; maximum at. ma. Example 1 Example If S--CCH=NON= CH C S HCC-CH:N-OC N=GH-CCH 8:!) -'--O1ElI 5 EEO-4") 1"-OH HO 'C[ 5.03

' this 23115 While following the procedureof, Examplei,

" 02 gram of benzidine. and 1.0. gram of. 3 ace ani 3 A mixture of: 3.2 grams (0.01 mol) of 5-acetlidomethylene-5-methyl-thi0ph i- -0 6 were lieanilido-methylene-3-allylrhodanine, 0.6 gram acted in 15. cc. of isopropyl alcohol in the presence (0.005 mol+10%) of p-phenylenediamine, cc. of several drops of triethylamine. The resulting of isopropyl alcohol and 0.5 cc. of triethylamine T5 dyev sensitized a silver: chlorobromide emulsionfto' was refluxed on asteam bath for about 1 hour. 520 mp, with a maximum at 480 m a 'Exampzevn moo-o-cH=N-C -N=on-c c-cm 1 -OH Holt 3- 7. $41K; 56H! 3.0 grarns of 4-acetanilidomethyleneel-phenyl- 3-methyl -5-pyrazolone and 0.5 gramof p-phen ylenediamine were reacted together cc. of isopropyl alcohol in the presence of 2}; few drops of triethylamine. The resulting dye sensitized a C-OH fogm ch lporobromide emulsion to 526m with a (QHtlaN-HC maximiii ij t 1 me- Example VIII I c n I l-H 110- =0 1.0 gram of p-phenylenediamine and 4.0 grams v of fi-aidtainilidomethylene-B-phenyl?2,4-thiazoledione were reacted in 150 cc. of'isopropyl alcohol in the-presence of 1 cc. of trietlqfylamine. The resulting dye sensitized a silverhlilorobromide emulsion to 530 m with a maximumat 510m t 50 Example IX allyl-rhodanine' and ethylene diamine were'dissolved in 250 cc. of isopropyl alcohol, and the mix ture refluxed for 1 hour. During this time, a yellow solid separated. After cooling, the reac-' tion mixture was filtered of! and the dye recrystallized from methanol. The dye sensitized a silver chlorobromide emulsion to 480 ma, with a maximum at 440 m (33115 Y J dam A'mixture or 6.0 grams of S-acetanilidometh: ylene 3-allylrhodanine, 0.5 gramof an 85% aqueous solution of hydrazine hydrate, cc. of isog propyl alcohol, and one drop. of triethylamine were refluxed for 1. hour. The pale yellow pre cipitate, which formed, was filtered off and boiled out with several portions of methanol. The insoluble portion was recrystallized from methanol. The dye sensitized a silver chlorobromide emul'-" sion to 470 m with a'maximum at 430 m A mixture of gra or fi -(v -jacetanilidoallyl ijdene) 2-diphenylaminoe3-ethyl 4 4(5) thiazo lone',"l.0'gram of p-phen'ylenediamine, 125 cc. of

isopropyl alcohol and 0.5 cc. of triethylamine were refluxed on a steam bath for about 1 hour, during which time the dye separated from the hot alcohol. The mixture was filtered while hot and the filter residue boiled outtwice with 100 cc.

1.0 gram o f p-phenylenediamine and 4.0 grams 0f .5-actanilidomethylene-3-pheiiyl-li-thiazoled re reacted in 150 cc. o1: isopropyl alco- I j dyesensitized a silver ehlorobromide emulsion-to 530 nm, with amaximum at 510 m Example X hol in presenceof'l cc. of triethylamine, The 6 portions of methanol. The dye was further purified by dissolving it in N/l-caustic solution, filtering the solution carefully and precipitating with dilute acetic acid.

Example XIII v 3.0' grams of 5-iacetanilidoinethylene).534 ethyl 2 thio-2,4(3,' 5) oxazoledione, and; 1,1 grams of 2,6-diamin'o-pyridine were mixed with 20 cc. of isopropyl alcohol containing 1 cc. of triethylamine. The mixture was boiled, under reflux, for 1 hours, cooled and then diluted with 15 cc. of water. .The dye which separated was boiled out twice with ethyl alcohol and then dried. Example XIV ,zaoezeramsi -;(resetanilidoallylidenel-fis ethylsl phenyhfi thiohydantoin and :l:.0 gram oi e nhenylenediarnine. were d ss lved 7:0 cc; of: isopropyl alcohol. ontainin about QC. of tri thylamine, and the mixture. heated under reflux ioriahout; -1. homx-v After; cooling to ro m tem-- perature, the mixture. was; filtered and the residue boiled out twice with 100 cc. or methanol.

Example ExamplaXVI- mixture of- 3.1 grams of 5-(y-acetanilidoallylidene) -2-thio 4,6 diketohexahydropyrimidine, 1.0 gram of p-phenylenediamine and 50 cc.of isopropyl alcohol and .1. drop of triethylamine were refluxed for 1, hour. The solid. which ire-- eipitated was filtered ofi. and boiledwith-several po tions of m thanol. 'lihe diagrammatic spectro r ms constituting. the. accompanying drawing illustrate the regions orthe spectrum to; whichv same-of the azanol dy s of; the present invention will sensiti a silver-chlorobromide emulsion containing about. 4-5%. of silver halide and the extent or the sensitization at various wavelengths. The five figures of this drawing illustrate the sensitizing properties of the dyes prepared in accordance with Examples 1 to 3 andTS to 6.

In the preparation of emulsions containing P I, l l

dye may be; dissolved :in 01;. and a. volume --of this. 5v to 50 milligrams added me -t di e m nt will e ounn m eachce e...

by a'fevv'"cornparative experiments. The dyes maybe added; to the emulsion in the form, of solutions';-.;Suitable solvents as indicated in the or ethyl alcohol which be anhydrous or diluted with a small "volume of water. In actual practice, the. dye'siire applied to: e ulsion during any stage'of its production. However,. they are preferably added to the finished emulsion before being cast.

The above-examples; are illustrative. chi-hand should not. beconstrued as limiting the, inven tion, since it will be apparent to those skilled-in the art that-the dyes of the present inven ion may. be incorporated into photographic. emuifi sions' by methods other" than those described herein. This appllcationis a division of our c opending application Serial No." 701,424, filed October 5, 1296, ow United States Patent 2 ,4 96,841, issued February 1950;

While thepresent invention has 'been described in considerable detail with reference "to'isertain preferred procedures, materials and uses it is un derstood that the new class of azanol dyes and usee sen i z dye smt l t st t.o, -an dthat numerous variationsand modified: tions. described in the foregoing specification may be made, as, for example, the dyes which contain a keto-heterocyclic nucleus, e. g., oxazoledione, hydantoin, and rhodanine nucleus, as illustrated a in Examplesul-3, 8-10, and 13-15 inclusive, may

. thiazole',h'avimg, a reactive'methyl groupinfthe a-position to the nitrogen atom in the presence" of a condensing agent'suchaspyridine, quinoline and the like. In thefirst-reaction (alkylation), the azanol dy'els'rhodified to the extent-that the nitrogen atom in the 3-posit-ion of the oxaiznledionej-hydantoin or rhodanine ring is quaternized and the sulfur atom in the 2-po'sition is converted to a thioether group. In the" second reaction (condensation), the alky-latedy azanol dye is condensed with a'cyclammoniumv base 0.2

where I N-XN and g e'have the' values as ove' R1 represents ani alliyl, 'alk o'r aryl radical, Re represents'alkyL'P and-Q, which may be the"sameor'difierent, represent the atoms necessary to..completea.,heterocyclic ringsystem of the type usual in cyaninedyes, e.'g.', indolenines, lepidines, oxazoles oxazoli'nes, selenazdjles, selena'zolines, pyridine, q t iinoline, thiazoles, thiazolines, diazoles and Ql-lIIIIaZOliIlBS such as benzthiazoles, ben-zselenazoles, naphthoresentsfa dye-precipiating acid radical of the examples am the alcohols, for instance, methyl 76 type gshal in cyanine dyes.

We claim: 1 1. A photographic light sensitive element which comprises a gelatino silver halide emulsion containing an azanol dye characterized by wherein A represents the atoms necessary -to complete a member selected from the class consistingof a 5-membered and G-membered heteroaliphatic, aromatic and heterocyclic primary diamines.

2. A photographic light sensitive element v which comprises a gelatino silver halide emulsion containing an azanol dyecharacterized by wherein A represents the atoms necessary to complete a member selected from the class consisting of a fi-membered and 6-membered heterocyclic ring system, n represents a positive odd integer of from 1 to 3, and Ar represents an aromatic radical containin up to 12 nuclear carbon atoms.

3. A photographic light sensitive element which comprises a gelatino ,silver halide emulsion containing a-n azanol dye as defined in claim 2, wherein Ar is phenyl.

4. A photographic light sensitive element which comprises a gelatino silver halide emulsion containing an azanol dye characterized by the formula:

\COH HO- I wherein A represents the atoms necessary to complete a member selected from the class consisting of a 5-membered and B-membered heterocyclic ring system, and n represents a positive Odd integer of from 1 to 3.

i0 5. A photographic light sensitive element which comprises a gelatino silver halide emulsion containing an azanol dye of the following formula:

$3115 6. A photographic light sensitive element which comprises a gelatino silver halide emulsion containing an azanol dye of the fOllOWil'lg formula:

, I (EaHn CaHA 7. A photographic light sensitive element which comprises a gelatino silver-halide emulsion containing an azanol dye of the following formula:

S--CCH=NN=CH-CS s= J C-QH -0 8. A photographic light sensitive element which comprises a gelatino silver halide emulsion containing an azanol dye of the following formula:

( u a dHll tam ALFRED w. ANISH. LEE 0. HENSLEY.

No references cited. 

1. A PHOTOGRAPHIC LIGHT SENSITIVE ELEMENT WHICH COMPRISES A GELATINO SILVER HALIDE EMULSION CONTAINING AN AZANOL DYE CHARACTERIZED BY THE FORMULA: @SP 